Organic detergent compositions



Patented Feb. 5, 1946 ORGANIC DETERGENT COMPOSITIONS Russell Park McGhie, B1-ooklsm, N. Y., assignor to Colgate-Palmolive-Peet Company, Jersey City, N. .L, a corporation of Delaware No Drawing. Application May 19, 1942,

Serial N 443,638

g 9 Claims. The present invention relates to a process of making detergent compositions and, more particularly, to a process of preparing sulphated and sulphonated organic materials having good wetting, emulsifying and deterging properties, and

to the novel product of said process.

Synthetic detergents, particularly those comprising sulphated and/or sulphonated organic compounds, have been made and used for many years, but one of the great difllculties in their manufacture has been the tendency of the masuch as tanks, drying rolls, spray nozzles and the like, especially those made of iron and steel. This tendency, which is particularly objectionable in compositions having a pH below 7.0, not

only results in pitting and corroding away of metal parts, but also causes discoloration of the product and a decrease in its ability to produce foam. The product, as heretofore produced, cannot be stored in metal vessels, except in stainless steel tanks or other expensive corrosionproof alloys, without corroding the containers. Even though the containers are lined, enamelled, painted or nickel plated, they are still unsuitable for storing this material, as the wetting power of the solution is often so great as to penetrate the minute pores of they coating, loosening the coating from the metal and corroding the metal walls, and as the lining or coat- "ing often cracks or breaks for one reason or another to expose the metal wall beneath. Moreover, the action of the sulphonated material upon the metal introduces impurities which result in deterioration of the product, both in color and in clarity of aqueous solutions prepared therefrom.

It is an object of the present invention to provide a process for manufacturing detergent compositions of high clarity and good color stav bility in aqueous solution.

It is another object of the invention to provide a process of manufacturing sulphated and sulphonated organic materials of light colorwithout corroding ordinary metal apparatus.

It is also an object of this invention to pro- I invention will be apparent from the following description. 7

According to this invention, it has been found that the addition of a small'proportion of an inorganic phosphate to non-soap detergents, emulsifiers and wetting. agents of the type of sulphated or sulphonated organic materials provides a composition which in aqueous solution is clear, color-stable and highly soluble and which is substantially non-corrosive. The use of inorganic phosphates with detergent materials of this type has been taught by the prior art but for a different purpose, requiring different and necessarily larger proportions, Earlier experimenters and investigators employed phosphates in sumcient amount to be effective as adjuvant washing, cleansing, emulsifying and wetting agents and/or for increasing the alkalinity of the composition. It is an unexpected feature of the present invention that the addition of an amount of phosphate equivalent to about 0.001% to about 0.5% of the weight of sulphonated (true" sulphonated and/or sulphated) material, an amount which is so low as not to modify the detergent properties of the sulphonate nor'substantially to alter the pH of the composition, can still provide unusual results in giving very clear, color-stable compositions which stantially non-corrosive.

The sulphated or sulphonated organic compounds comprised by the novel compositions of the invention may be prepared from organic materials which are applicable for sulphonation (true' sulphonation and/or sulphation), especially those having about eight to about twentysix (and preferably about twelve to about twenty) carbon atoms'to the molecule, including fatty oils, unsaturated fatty acids, mineral oils, mineral oil extracts, monoand di-glycerides, partial esters or ethers of polyglycols, esters or ethers of glycols, polyglycols and polyalcohols, aromatic and alkylated aromatic compounds, alcohols and olefines, coal tar distillates, and numerous other organic compounds and mixtures of compounds. Such compounds can be sulphonated by any of several methods and may form any of several products, depending upon the method of sulphonation employed. The sulphated or sulphonated organic compounds include sulphonated mineral oil; conventional mineral oil refinery sludges; sulphonated mineral oil extracts, including the products described in U. S. Patents Nos. 2,149,661, 2,149,662 and 2,179,174; sulphonated fatty acids and oils, including sulphonated castor oil, sulpho-ricinoleic acid, sulphonated olive oil, and sulpho-oleic acid; aliphatic 'sulphonates and sulphates, including cetyl sulphuric acid, dodecyl acid sulare subphate, and tetradecanehydroxy sulphonic acid- 1,2; aliphatic ether and ester sulphonates including the dodecyl ether of hydroxy ethyl sulphonic acid, the cetyl ether of glyceryl sulphonic acid, tallow monoglyceride monosulphate, and coconut oil fatty acid monoesters of beta methyl glycerine sulphonic acid; sulphonates prepared by treatment of organic materials with sulphur dioxide and chlorine in the presence of light and hydrolysis of the product; sulphonates prepared by treatment of organic bodies with sulphuryl chloride and an activating agent in the presence of light and hydrolysis of the product; fatty acid amides of amino alkyl sulphonic acids, including lauric amide of taurine and tall oil acid amide of amino glyceryl sulphonic acid; sulphonic acids of naphthenes and naphthenic acids, lignin sulphonic acids; aromatic and properties, higher percentages of phosphate, say. up to about 3%, or up to about 5% or even higher.

may be added, without losing the other advantages described herein. -When using a small amount of phosphate in the preferred range, the' phonated materials are intended for use in dye baths and the like, a large proportion of phosalkylated aromatic sulphonic acids, including sulphonated while dissolved in liquid sulphur dioxide; and innumerable other organic sulphonic and sulphuric acid derivatives or mixtures thereof. These organic sulphate and true sulphonate compounds include those in which the organic radicals of the molecule are unsubstituted or those which contain substituents such as halogens, halogenoids, hydroxyls, nitrogen containing groups, acyl groups, acyloxy groups, alkoxy groups, etc. Of these sulphated and sulphonated materials, the most suitable for inclusion in the novel compositions of the present invention are normally non-alkaline, and especially those having carboxylic ester linkages, including the sodium salts of the sulphuric acid esters of coconut oil fatty acid monoglycerides, tallow diglyceride monosulphate, and stearyl monoesters of beta methyl glycerine sulphonic acid.

The inorganic phosphates, which may be added to sulphated and/or sulphonated compounds to achieve the desirable results described, are watersoluble phosphates, including primary, secondary and tertiary sodium orthophosphate and the sodium salts of tetraphosphoric, tripolyphosphoric and pyrophosphoric acids, wholly or partially neutralized, as well as the other alkali metal and ammonium salts of orthophosphoric, tetraphos phoric, tripolyphosphoric and pyrophosphoric acids, wholly or partially neutralized. It is preferred to use salts of phosphoric acids capable of forming water-soluble calcium salts. Any one or more of the phosphates mentioned above may be incorporated in the compositions of this invention, and/or other compounds breaking down or reacting with the sulphonated materials to provide said phosphate salts may be employed.

Where the sulphonated compounds are to be non-- dom from corrosive effect, good color stability,

high solubility and improved foaming, without substantial modification of the detergent and other desirable properties of the active ingredient. Where it is permissible to modify the detergent phate salts introduces undesirable ions in objectionable amounts. The inorganic phosphates may be added during any step of manufacture of the sulphonated materials or may be added after completion of the preparation. The addition of the small amounts'of phosphates described stabilizes the material in storage in metal tanks and in drums for shipment. This advantage is particularly apparent in concentrated solutions of the sulphonates, say, in aqueous solutions containing about 5% to about 50% of active ingredient, where the art may now dispense with the former practice of employing only stainless steel or non-metallic containers.

The manufacturing process is greatly improved by introducing the inorganic phosphate, in any proportion, at a point in the manufacture prior to the hydrolyzing and/or neutralizing step. While the proportion of phosphate to active ingredient is advantageously low in the final product to avoid modification of detergent properties, it is desirable to employ larger proportions, say, of the order of about 10% to about 50% and even as high as 100% or higher, during manufacture to avoid corrosion of metal equipment.

The neutralizing step may be carried out in batch operation or continuously and/or in the presence of previously neutralized material, and water or aqueous solutions of salts and/or acids or alkalies inay be used therefor. Alkaline agents are most commonly employed, a sulphonate salt resulting from the neutralization, and agents suitable therefor include sodium and potassium hydroxides, carbonates, silicates, etc., pyridine. methyl morpholine, piperidine, alkyl amines, alkanolamines and other organic and inorganic bases and alkaline materials, and mixtures of these. The alkaline agent may be introduced in aqueous solution, in alcoholic solution, or in solutions of other solvents, or may be substantially anhydrous and/or substantially undiluted. The amount of solvent introduced with the alkaline or saponifying agent has a bearing upon the water or organic solvent content of the finished product.

The neutralization may be carried out by intimatelymixing sulphonated material with an alkaline agent in the presence of inorganic phosphate in a reaction vessel under atmospheric,

superatmospheric or reduced pressure. The inorganic phosphate may be admixed with the sulphonate salts thus formed by introducingit into the reaction mixture in the sulphonating vessel. either separately or mixed with the sulphonating agent, and/or it may be admixed by mixing the phosphate with the sulphonated material and/or the neutralizing agent befdre contacting, and/or by simultaneously passing into the neutralizing vessel a solution containing phosphate salts.

When adding the phosphatic material prior to neutralization, the phosphoric acids corresponding to the phosphate salts hereinbefore described as suitable for use in the new compositions oi the inventionmay replace all or part of the phosphate salts. However, when employing a phosphoric acid, especially during the sulphonating step, theproportion of phosphoric acid to sulphonating agent must be sufliciently low to avoid phosphation of a substantial amount, if any, of

- the neutralizing'vessel may be provided, as desired. Where the product is to be dried, heat may advantageously be supplied to the reaction mixture in the neutralizing vessel. The heat of neutralization may alone be suflicient to raise the mixture to the desired temperature, depending upon the materials employed and the subse-' quent operating conditions, or heat from external sources may be supplied. Either or both of the reactants may be preheated by steam or other means before being run into the-vessel and/or the mixture may be heated during and/or after admixture. The neutralization step may also be operated in conjunction with a spraying step for obtaining substantially granular and/or hollow particles, the material from the reaction vessel being forced in fluid form into a spinner bowl or spray nozzle, and, upon atomization, coming in contact in a spray tower with a current of inert gas, preferablyair. The air current may be heated, and it is preferably passed through the tower cbuntercurrent to the sprayed material, although concurrent passage of the air is also contemplated. I

Another method of neutralization is to mix the pipes and nozzles, because the aqueous mixture reactants in a mixing vesel with inorganic phosphates, and then to pass the neutralized product containing phosphate salts to a vapor separation chamber at a lower pressure. The sulphonated material and neutralizing agent may also be reoperating preferably continuously, the neutralized sulphonate salts and the phosphates can be discharged to a low pressure zone, preferably through a constricted outlet or nozzle. Heat may be supplied to the pipe, if necessary, to raise the temperature of water or other solvent therein to the vaporization point at the pressure within the pipe, and the temperature and pressure at any point in the 'pipe may be kept substantially constant or may be varied in a cyclic manner for the purpose of creating greater turbulence in the reaction conduit by alternately establishing and destroying a vapor phase therein. Upon flashing into the lower pressure zone, the heat of the reaction product is employed to vaporize the water or other solvent atthe low pressure of the separation chamber, and the vaporized material goes off at the top. while the sulphonate salt containing phosphates mixed therewith and having at least a portion-of water and other volatile materials removed, falls to the bottom.

By contacting the neutralization mixture, mo-

mentarily and Just before discharge into the low pressure flash zone, with an inert gas-at a considerably .higher temperature, less heat need be supplied to the neutralization and preheating conduit and/or a higher absolute pressure may be employed'in the separation chamber. The contact of the reaction mixture with an inert gas. such as superheated steam, kerosene vapor; carbon dioxide, flue gases, stack gases, etc., is preferably made at extremely high velocity and for a minimum time period before introduction into the flash chamber. The contacting can be advantageously accomplished by a nozzle designed to permit intimate but only momentary direct contact and a minimum of indirect contact before admission into the flash chamber. Employing this modification, the length of the hydrolyzing and/0r neutralizing conduit can be appreciably shortened, if desired, and less heat need be supplied thereto by external heating of the conduit and/or by preheating of the sulphonated material and/or the neutralizing agent.

In another procedure, it is possible, by means of superheated steam or other inert gas, to supply sufficient heat at an optimum temperature and velocity in order to effect instantaneous hydrolysis and/or neutralization along with flash distillation of the materials to be withdrawn as, a vapor. This procedure avoids plugging of is not under flashing conditions for any appreciable time before introduction into the nozzle, where it attains high velocity and adequate heat in momentary time before its discharge into the fiash chamber.

Although the present invention is especially directed to concentrated solutions of the novel compositions provided, the proportions of superheated steam introduced into the nozzle in these various modifications can be so regulated in practice that a dry product or a hydrated product of any degree of hydration can be produced. The product may be made in a more or less finely divided condition, which permits its ready transformation into flakes or other physical forms, for example, by passing between a pair of properly spaced rolls, or by pressing into cakes, or by other means, with or without addition or modifying agents.

The presence of inorganic phosphates during neutralization and subsequent operations substantially prevents corrosion of metal parts of apparatus and equipment, including mixersand tanks, pipe lines and conduits, spray nozzles, spinner bowls, drying rolls, etc., even at the higher temperatures disclosed. Furthermore, due to the presence of the phosphates, the product retains its original color.

Adjuvant materials may be admixed with the sulphonate salts containing a small proportion of phosphates thus formed by mixing the adjuvant materials with the sulphonated organic compounds and/or the neutralizing agents before neutralization or flashing, by simultaneously flashing a second solution containing such adjuvant materials, and/or by mixing the final product therewith. Such adjuvant materials may include fatty acid soaps, resin acid soaps, naphthenic and alkylated naphthenic acid soaps, alkaline soap bui ders, additional water-soluble, watersoftening compounds of acids of phosphorus, and other salts including so ium carbonates, sodium silicates, borax, sodium icarbonate, sodium sulborate, sodium tartrate, sodium citrate, sodium oxalate and the corresponding ammonium, substituted ammonium and potassium salts of the corresponding acids; insecticidal, germicidal,

styptic and medicinal agents,'including aluminum chloride, mercuric chloride and various copper and lead salts; coloring agents, abrasives, fillers and water-dispersible gums, including dyes, lakes, pigments, silica, kieselguhr, silica gel, feldspar, precipitated chalk, pumice, infusorial earth, bentonite, talc, starch, Irish moss, sugar, methyl cellulose, agan'gumtragacanth, gum arabic and polyvinyl alcohol; liquids, such as ethyl alcohol, glycerol; cyclohexanol, naphtha, benzene, kerosene, turpentine, pine oil, decalin, and tetralin, and the like. The type of addition agent will depend upon the ultimate use of the new com-' position. i g

The following examples, described herein, are merely illustrative of the present invention, and it will be understood that the invention is not limited thereto.

- Example I About 154 pounds of pyrophosphoric acid is dissolved .in about 666 pounds of fuming sulphuric acid oi. about 102.8% strength. The acid mixture is then mixed with about 33 pounds of anhydrous (about 99.5%) glycerine in a mixer of ordinary steel and equipped with cooling means to keep the temperature at about 30 C. The resulting mixture is then passed to a similar mixer and is there mixed with about 216 pounds of coconut oil and about 272 pounds of tallow, heating during the mixing operation to about 50 C. a The agitation is continued for about forty minutes, after which the reaction product *is passed to a neutralization tank of ordinary steel and is there mixed with about a 30% aqueous solution of caustic soda. The product is brought to a pH of about 6.0 to 7.0 and comprises a mixture of tallow and coconut oil diglyceride monosulphates with sodium sulphate, containing an amount of sodium pyrophosphate equivalent to about 15% of the weight of the tallow and coconut oil diglyceride monosulphates.

Example II Coconut oil monoglyceride monosulphate is prepared in accordance with the disclosure set forth in U. S. Patent No. 2,130,361 to Muncie. This active organic ingredient, as prepared, is disposed in a mixture in the proportion of about 40 parts of said active organic material toabout 60 parts of sodium sulphate, and this mixture is dissolved in water to form an aqueous solution containing about 40% of solids. Disodium orthophosphate in an amount equivalent to about 0.3% by weight of the active ingredient is added to the solution. The resulting solution is clear and of a light color and can be shipped in metal containers without danger of corroding the same.

Example III aso asao 50% ct mineral oil sulphonyl chlorides. The crude material thereby formed is simultaneously purified and extracted with about 2 parts of liquid sulphur dioxide, the liquid sulphur dioxide phase 6 being continuously removed. The sulphonylchlorides contain some of the unsulphonated oil, and separation can be accomplished by re-extracting the sulphur dioxide solution with ligroin. The sulphur dioxide is then removed, and about 1 2,25 parts of syrupy pyrophosphoric acid having about 82% phosphorus pentoxlde is added to the residue. The resulting mixture is hydrolyzed and neutralized by stirring with an aqueous 30% solution oi sqdium hydroxide at a temperature 0! about 90 0., and the mixture is diluted so as to contain about 10% oi the sulphonated product. The sulphonate solution is treated with sulphuric acid to neutralize excess alkali, thus forming a certain amount of sodium sulphate. Additional sodium sulphate is also added to bring the salt content to a desired proportion. The solution is passed to steam-heated drying rolls of ordinary steel, and a flaky, snow-white product is obtained.

Ezjample IV Patent No. 2,149,661 to Brandt. Following the procedure described therein, a dry, fiuiiy powder is obtained, and this is dissolved in water to form an aqueous solution containing about 15% of the active sulphonated mineral oil extract. An

amount of sodium tetraphosphate equivalent to about 0.2% of the weight of the active ingredient is added to this solution. The solution thus produced is clear and almost colorless and can be stored and shipped in ordinary steel tanks.

The use of the term "sulphonated with reference to organic compounds in the following claims will be understood to include sulphated as well as true sulphonated materials. Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications of this invention can be made and that equivalents can be substituted therefor without departing from the principles and true spirit of the invention. Such variations and modifications are believed to be within the scope of the present specification and within the purview of the appended claims.

I claim:

1. As a new composition oi matter, a non-soap detergent comprising a sulphonated organic compound having an inorganic sulphur-containing radical bound to an aliphatic carbon and having a pH in aqueous solution below 7.0, and an amount of a water-soluble inorganic phosphate about 0.001% to about 3% by weight of said sulphonated organic compound, said composition providing a clear aqueous solution which is color- 65 stable and substantially non-corrosive to ironcontaining metals.

2. As a new composition of matter, a non-soap detergent comprising a sulphonated organic compound having an inorganic sulphur-contain ing radical bound to an aliphatic carbon and having a pH in aqueous solution below 7.0, and an amount of a water-soluble inorganic phosphate about 0.001% to about 0.5% by weight of said sulphonated organic compound, said com- 75 position providing a clear aqueous solution which stable and substantially non-corrosive to ironcontaining metals. r

4. As a new composition of matter, a non-rsoap detergent comprising alkali metal salts of the sulphuric acid esters of coconut oil fatty acids monoglycerides, and an amount about 0.001% to about 3% by weight of said alkali metal salts of a water-soluble inorganic salt of a phosphoric acid capable of forming a water-soluble calcium salt, said composition providing a clear aqueous solution which is color-stable and substantially non-corrosive to iron-containing metals.

5. As a new composition of matter, a detergent comprising a mineral oil sulphonate produced by treating a mineral oil with sulphur dioxide and chlorine in the presence of actinic light and substantially neutralizing the product of said treatment, and an amount of a water-soluble inorganic phosphate about 0.001% to about 3% by weight of said mineral oil sulphonate, said composition providing a clear aqueous solution which is color-stable and substantially non-corrosive to iron-containing metals.

6. A clear, color-stable non-corrosive aqueous solution having a pH below 7.0 and comprising water, a sulphonated organic compound 'having an inorganic sulphur-containing radical bound to an aliphatic carbon and an amount of watersoluble inorganic phosphate about 0.001% to about 3% by weight of said sulphonated organic compound.

'7. A clear, color-stable non-corrosive aqueous solution having a pH below 7.0 and comprising water, a sulphonated organic compound having an inorganic sulphur-containing radical bound to an aliphatic carbon and an amount of a watersoluble inorganic phosphate about 0.001% to 'about 0.5% by weight of said sulphonated, or-

ganic compound.

8. A clear, color-stable non-corrosive aqueous pound.

9. As a new composition of matter, a detergent comprising an alkali metal salt of a sulphonated aliphatic compound having about twelve to about twenty carbon atoms to the molecule and having an inorganic sulphur-containing radical bound to one of said carbon atoms, and an amount of a water-soluble inorganic phosphate about 0.001% to about 3% by weight of said alkali metal salt, said composition providing a clear aqueous solution which is color-stable and substantially noncorrosive to iron-containing metals.

RUSSELL PARK MCGHIE. 

